The present invention pertains to insulated door assemblies having compression molded skins which exhibit minimal thermal deflection. More particularly, the subject invention pertains to insulated door assemblies having skins of compression molded, moderately dark colored, fiber-reinforced sheet molding compound which exhibit reduced thermal expansion and contraction, which retain the ability to receive pigmented stains in a uniform manner, and to improved processes for their preparation.
Entry door system containing fiber reinforced compression molded door skins are becoming increasingly popular. An example of the latter is the Classic-Craft(trademark) door available from Therma-Tru Corporation. Such entry door systems contain front and back skins which are generally both prepared from fiber reinforced sheet molding compound which has been compression molded to provide a wood grain pattern on the door skin. These door skins are mounted onto stiles and rails and contain highly efficient thermal insulation between the skins. Examples of such door assemblies may be found in U.S. Pat. Nos. 4,550,540 and 5,537,789. Such door entry systems are much more thermally efficient than solid wood doors or insulated metal doors, as well as being more aesthetically pleasing than the latter.
However, the increased thermal efficiency of such doors is a mixed blessing, often being so effective in reducing thermal transmission from the exterior to the interior that temperature differentials of 55-60xc2x0 C. may be created between the exterior and interior skins. In such cases, the skin exposed to the higher temperature will expand to a greater degree than the skin exposed to the lower temperature environment. A portion of this expansive force may be resisted by the adhesive which adheres the skin to the frame; by the frame itself; and by the insulating core. However, stresses on these door components increase dramatically as the temperature differential between opposing skins increases. The stresses can be so great as to temporarily warp the door assembly in a phenomenon known in the industry as xe2x80x9cthermal deflectionxe2x80x9d. Consumers, as can be imagined, are generally distraught when they observe this behavior. In addition, the warping or bowing which the door experiences may be of such magnitude that contact between the weatherstripping and door assembly may be lost, thus allowing considerable air infiltration and associated thermal loss.
When thermal deflection occurs, discerning consumers find the products unacceptable in insulated entry door assemblies of even typical residential height, for example, those of about 2 m (6 feet) in height. These doors have lock edges termed xe2x80x9clock stilesxe2x80x9d of which the section above the lock may be viewed simplistically as a cantilevered beam approximately 1.1 m in length. Attempts to minimize thermal deflection have been centered on structural changes to the door support members. For example, structural modifications on typical residential insulated door assemblies may use laminated beams in the lock edge or lock stile to reduce thermal deflection. However, the use of such laminated beams results in significant increase in raw material cost. Moreover, such efforts have not been entirely satisfactory, and thermal deflection continues to be a design issue in such products.
While thermal deflection has been a considerable problem in entry doors of normal height, when taller doors are used as dictated by recent trends in building products, the problem becomes even more severe. In such taller doors, the lock position remains at a relatively stationary height, i.e., a height convenient for grasping with the hand of the hypothetical xe2x80x9cnormalxe2x80x9d individual. However, the increased height thus requires a considerably longer portion of the door to be located above the lock set. Thus, the combination of increased skin surface area generating greater force, and a longer cantilevered length, results in a magnitude of thermal deflection which is unacceptable for such doors, even those containing laminated beams in the lock stile.
Numerous materials exist which could be substituted for the fiber reinforced sheet molding compound used to make fiber reinforced door skins. Unfortunately, however, the materials of which the door skin is constructed must meet numerous criteria other than merely minimal thermal expansion. For example, the skins must be relatively strong and yet must have appreciable resiliency in order that they may survive the destructive forces generated upon thermal expansion. Further, and more importantly from a commercial aspect, the door skins must be capable of receiving a pigmented stain in a uniform manner, and should also be capable of being economically pigmented to produce a medium dark to dark surface prior to staining and finishing.
For example, early xe2x80x9cfiberglassxe2x80x9d doors were colored white. The white substrate was visible through the thin films of solid color stains used to achieve an appearance of wood. Discerning customers found the substrate color to be unacceptable. Moreover, at locations of the door experiencing wear, the underlying white surfaces are easily exposed, rendering the door aesthetically displeasing. Since about 1984, most manufacturers have pigmented the molding compounds used to compression mold the skins with dark or medium darkness pigments. Thus, the materials of skin construction must be capable of receiving such pigments and also of receiving a stain coating in a uniform manner. Furthermore, the materials of construction must be relatively economical in order that the door systems may be made available at a reasonable price. For these reasons, fiberglass sheet molding compound, consisting predominately of curable unsaturated polyester resins generally incorporating one or more co-curable unsaturated monomers, continue to be used to manufacture textured, compression molded door skins.
In the preparation of molded articles by the compression molding of unsaturated polyester/co-curable unsaturated monomer compositions, considerable shrinkage results during the molding process due to a volume decrease in the curable ingredients as these react and crosslink. In non-textured articles, the result may be a cured product which no longer has the dimensions of the mold. In textured articles, the decrease in volume may produce articles with insufficient or indistinct texture. Addition of shrink reducing adjuvants have been found to lower the propensity of the curing polymer system to shrink, thus allowing for full definition of textured surfaces. The efficacy of shrinkage control adjuvants may be assessed by visually observing surface texture, or by measuring the dimensions of cured articles and comparing them to mold dimensions. As the dimensional coefficient of thermal expansion is generally not a linear function of temperature, the expansion and contraction of a cured, finished product over the temperature ranges expected of exterior doors cannot be predicted from measurements made based on compression molding temperatures. Furthermore, those skilled in the art of sheet molding compounds have not been concerned with the thermal expansion of cured, finished products per se, only with changes in volume which are the result of curing during the molding process.
Use of sheet molding compound containing low profile additives was disclosed in low linear thermal coefficient expansion moldable materials in Assignee""s U.S. Pat. No. 5,537,789. However, the low profile additive was deemed important to minimize shrinkage of the hot and partially cured skin during molding. There is no recognition apparent from the ""789 patent that the low profile additive had any effect on either the linear thermal coefficient of expansion itself or the ability of a door made from compression molded sheet molding compound to resist thermal deflection.
It has been discovered that reduction of the thermal expansion of compression molded door skins prepared from unsaturated polyester sheet molding compounds over the temperature extremes expected during normal use can be accomplished through the use of the same so-called xe2x80x9clow profile additivesxe2x80x9d useful in retaining mold texture definition during compression molding. Low profile additives may be defined as relatively polar thermoplastic polymer materials which, when added to sheet molding compositions, encourage the formation of numerous microvoids. Such additives are believed to phase out during cure under compression molding conditions, resulting in a multi-phasic polymer system. The phase-out of the low profile additives may increase the volume of the curing mass, offsetting the volume reduction of the curing and crosslinking unsaturated components. Moreover, the different phases appear to exhibit different degrees of contraction upon cooling. As the compression molded skins cool prior to and after their removal from the mold, the different phases contract at different rates, causing numerous microvoids to be created.
The microvoids have been found to aid significantly in reducing the thermal expansion of the finished door skin. Moreover, the microvoids are believed to assist in the creation and propagation of microcracks under stress, which adds to the resilience of the door skins, facilitating their continued adhesion to the door support components. Nevertheless, the use of low profile additives, while decreasing the thermal expansion exhibited by door skins, does not eliminate the expansion altogether. Moreover, when the same sheet molding compounds are used on taller doors, the thermal deflection which results from high temperature differentials is again unacceptably large.
Increasing the amount of low profile additive is effective in reducing the degree of thermal expansion of door skins over normal use temperatures. However, the increase in the number of microvoids creates a porosity problem in the skin surface which manifests itself by a mottled, uneven appearance of a stained skin. This mottled appearance is aesthetically displeasing, and unacceptable to the consumer. Therefore, merely increasing the amount of low profile additive cannot solve the thermal defection problem, as the increased amount of low profile additive cannot solve the thermal deflection problem, as the increased amount of low profile additive creates other problems.
A second means of reducing thermal expansion during compression molding is through the use of shrinkage control additives. While shrinkage control additives have been used in formulating sheet molding compound for use in manufacture of compression molded door skins, use of such additives has been very limited in terms of composition amounts. Such additives were introduced, as is the case with low profile additives, for minimizing thermal contraction in compression molded materials during cure. It is not known with certainty how shrinkage control additives function. For example, such materials may create a minor volume (quantity) of microvoids, but not nearly the volume associated with the microvoids produced with low profile additives. Moreover, while low profile additives tend to be highly polar polymers, shrinkage control agents tend to be non-polar. For example, common shrinkage control additives are polystyrene, polyethylene, polycaprolactone, and the like, whereas typical low profile additives include polyacrylics such as polymethylmethacrylate, polyvinylacetate, and saturated polyesters having relatively short aliphatic carbon chain lengths.
Entry doors are made in many styles. Currently, many doors which are to have a xe2x80x9cpaneledxe2x80x9d look, i.e., to be structured so as to mimic the traditional rail/stile/panel wood construction, have been produced in the same manner as flat, non-paneled doors. Following production of the flat door, the (traditionally) six panels are introduced by cutting holes in the door following a template, and assembling two-part panels over these holes. The panel halves are secured to each other by screws or press-in plastic fittings, thus xe2x80x9csandwichingxe2x80x9d the door between them.
This process of preparing paneled doors has several notable drawbacks. Firstly, the process requires molding of two relatively intricate panel shells, one for each side of the door. The intricate patterns generally require injection molding, and thus the panels will constitute a different material, an injection-moldable thermoplastic, than the sheet molding compound used to prepare the door. Because of the different materials, the stainability of the door and the panels will not be the same. The different color and depth of color due to differences in stainability are immediately noticeable to an observer. Achieving the same color for both parts is time consuming and fraught with error. Secondly, the holes required to be cut to receive the mating halves of the panels severely reduces the strength of the door. Finally, removal of the cut out sections involves removal of the insulating core of the door in these areas as well. Thus, the insulation efficiency decreases markedly.
The use of SMC materials, particularly those containing the combination of low profile additive and low shrinkage additive as described herein allow the preparation of aesthetically pleasing door skins in a reasonable amount of time. Thus, the overall cost of the door skins is maintained at an affordable level. If the curing of the SMC could be accelerated, increased production rates and further lowered costs would be possible. An increase in curing catalyst level should increase the curing rate. However, increased catalyst loading also increases the propensity for the SMC to prematurely cure. A reasonable shelf life for the SMC therefore precludes merely increasing the catalyst loading.
Increasing the amount of catalyst coupled with addition of inhibitors can produce systems which cure at reasonable rates yet offer reasonable shelf life. However, it has been noted that addition of inhibitors also generally reduces the ultimate cure level, i.e. the degree of crosslinking which may be achieved. xe2x80x9cCuring percentagexe2x80x9d is an indicator of the completeness of the cure. With t-butylperoxybazote catalyst and no inhibitor, for example, typical door skins and other parts exhibit a percentage of cure of about 88-90% at an 85 second demold time. Addition of increased amounts of catalyst along with an inhibitor increases the rate of cure, but the percentage of cure decreases. Suppliers of SMC have proposed the use of catalyst mixtures to speed processing, for example a mixture of t-butylperoxybenzoate and t-butylperoctoate. However, well cured parts retaining uniformly stainable characteristics could not be produced from this catalyst mixture. It would be desirable to provide SMC which has acceptable shelf life; which is faster curing than SMC employing t-butylproxyberzoate curing catalyst; which exhibits similar or better percentage of cure; and which, following cure, is uniformly stainable.
In molding stainable door skins and other parts employing SMC, in general a xe2x80x9cstackxe2x80x9d of SMC materials of the proper weight is placed into the center of the mold, and the mold closed while heating. The combination of heat and pressure causes the SMC material to flow throughout the mold. Pressure is maintained until cure is effected.
In some cases, blistering and other cosmetic surface defects may be produced during molding. It is known that after the SMC material has flowed to fill the mold, vacuum may be applied. The vacuum tends to reduce surface non-uniformities. Unfortunately, the use of vacuum also produces a xe2x80x9cscumxe2x80x9d on the surface. This scum is not pigmented to the same degree as is the SMC material, thus presenting a non-uniform surface color. Moreover, the xe2x80x9cscumxe2x80x9d does not accept stain in the same manner as the SMC material. Thus, the doors cannot be acceptably stained.
It is believed that the xe2x80x9cscumxe2x80x9d is produced as styrene monomer and low molecular weight oligomers volatilize from the resin and accumulate on the mold surface, where they polymerize. Polymerization inhibitors which may be present are of higher vapor pressure and are left within the matrix, facilitating the polymerization at the surface of the mold due to their absence, as the constituents migrate unevenly. The polymerized scum on the tool surface is scraped off as the SMC material flows in the mold during the pressing operation. The accumulation, which is darkened and discolored relative to the remainder of the SMC is thus distributed unevenly over the molded door skin surface. The loss of styrene monomer and low molecular weight oligomers increases the effective concentration of less volatile inhibitors, resulting in less complete cure of the molded skin.
It would be desirable to provide fiber reinforced insulated door assemblies having fiber-reinforced door skins, preferably textured, and most preferably, wood-grained skins, which can be economically manufactured from sheet molding compound, and yet which exhibit low thermal deflection due to the use of skins having low thermal expansion coefficients. It would further be desirable to provide skins suitable for such door assemblies which are able to be pigmented with medium to dark colored pigments, and which can accept pigmented stains in a uniform manner without the necessity for use of a pre-stain sealer. Such doors have not been heretofore available.
The present invention pertains to insulated, fiber-reinforced door assemblies, suitable for exterior use, which preferably exhibit minimal thermal deflection, even in doors of greater than normal height. The doors of the present invention contain fiber-reinforced door skins prepared from sheet molding compound which contains a resin system consisting of one or more curable, unsaturated polyester resins, one or more co-curable, unsaturated monomers, a low profile additive, and a microvoid-reducing thermoplastic polymer which is preferably a shrinkage control additive. Surprisingly, the door skins thus produced exhibit not only exceptionally low linear coefficients of expansion, but also are economically pigmentable, and capable of being stained by pigment-bearing stains in a uniform, aesthetically pleasing manner.
It has now been found that paneled doors can be produced simply without cutting holes in the basic door, by using a permanent, pressure sensitive adhesive to bond panels at the appropriate locations. Because the panels are flat and do not contain locating flanges, screw bosses, and the like, they may be made of the same material as the door skin. Thus, stainability mismatches no longer occur. Moreover, both the structural rigidity and insulation value increase, rather than decrease, when employing the adhesively bonded decorative panels. The same adhesives may be used to bond other trim as well. A preferred adhesive is VHB(trademark) Tape available from the 3M Company, which is believed to be an alkylacrylic co-polymer resin.
If has been surprisingly discovered that SMC employing a cure inhibitor in conjunction with a cure catalyst comprising t-amlyperoxybenzoate in major part ( greater than 50% by weight based on catalyst) not only allows a significant reduction in cure time (ca.40% reduction in cure time), but importantly, cure percentage is actually higher than non-inhibited t-butylperoxyberzoate systems, at 91-97%! Surprisingly, the skins produced with this inhibitor/catalyst combination are uniformly stainable.
It would be desirable to provide a composition which can be molded under vacuum to reduce surface defects, while retaining stainability. This problem is solved through use of the subject invention SMC employing inhibitor and t-amylperoxybenzoate catalyst. It is believed that the beneficial results achieved are due to the short cure time; i.e. cure times of less than 60 seconds, and preferably less than 50 seconds after mold closure. Thus, other combinations of catalysts and catalyst/inhibitor mixtures which enable cure of a door skin in less than 60 seconds can be used with vacuum in the subject process.
The fiber-reinforced door assemblies of the present invention include conventional door components such as lock stiles, rails, edges, insulation and the like, and two skins, at least one of which is a pigmented door skin according to the subject invention, this skin prepared from fiber-reinforced sheet molding compound comprising a curable, unsaturated polyester resin, one or more co-curable unsaturated monomers, a pigment, a low profile additive, a microvoid-reducing thermoplastic polymer, preferably of the class known to the art as low shrinkage additives, and fiberglass reinforcement. The sheet molding compound may also comprise fillers, viscosity adjusting agents, dyes, curing catalysts, and other customary ingredients. By the term xe2x80x9caxe2x80x9d as used herein with respect to a class of components is meant xe2x80x9cone or morexe2x80x9d. For example, the term xe2x80x9ca low profile additivexe2x80x9d means that minimally one low profile additive is employed, optionally two or more of such additives. Conventional door components are discussed in U.S. Pat. Nos. 4,550,540 and 5,537,789, which are herein incorporated by reference.
The curable unsaturated polyester resins are well known to those skilled in the art, and are generally prepared in a non-limiting sense, by esterification or transesterification of one or more unsaturated dicarboxylic acids or reactive derivatives thereof with one or more aliphatic or cycloaliphatic diols. Saturated dicarboxylic acids, aromatic dicarboxylic acids, or their reactive derivatives may be used in conjunction with the unsaturated dicarboxylic acid(s) to lower the crosslink density. Modification of polyester resins by reaction with dicyclopentadiene has been found to produce preferred curable polyesters for use in accordance with the present invention. Curable polyesters with moderately high to high crosslink density, i.e., a crosslink density lower than that obtainable from poly(ethylenemaleate) can produce skins with high resilience while maintaining strength characteristics. Curable polyester resins are available commercially, and are disclosed in U.S. Pat. Nos. 3,969,560; 4,172,059; 4,491,642; and 4,626,570, which are herein incorporated by reference.
The co-curable unsaturated monomers are also well known to those skilled in the art, and include, for example, the various alkylacrylates and alkylmethacrylates as well as vinyltoluene xcex1-methylstyrene, p-methylstyrene, and styrene, the latter being preferred. By the term xe2x80x9cco-curingxe2x80x9d is meant that the monomer contains reactive unsaturation capable of reacting with itself and/or the unsaturated sites of the curable polyester under the curing conditions. Additional co-curable monomers are identified in the above-referenced patents. A preferred curable unsaturated polyester/co-curable unsaturated monomer combination is a dicyclopentadiene-modified glycol maleate polyester and styrene monomer composition available from Alpha/Owens Corning under the product designation S-903.
Low profile additives are well known to those skilled in the sheet molding composition art. Low profile additives are generally relatively polar thermoplastic polymers such as polymethylmethacrylate, polyvinylacetate, various poly(alkyl)acrylate polymers and copolymers, and saturated polyesters, particularly those having a diol component of low molecular weight, such as ethylene glycol or diethylene glycol, i.e., a glycol having 2-4 carbons, optionally interspersed with ether linkages in the hydrocarbon chain. Low profile additives are generally recognized as creating microvoids in the cured product. While the mechanism of microvoid formation is not known with certainty, it is believed that during the cure of the curable polyester and co-curable monomer to form a thermoset structure, a microgel phase is formed from the curing/crosslinking of the unsaturated components which is at least partially incompatible with the low profile additive, which begins to phase-separate. The phase separation causes an increase in volume of the composition which partially or wholly offsets the shrinkage which results from curing of the polyester/co-curable monomer. The curing polyester forms a matrix which at least partially surrounds the low profile additive phase. Upon cooling, the differences in volume contraction between the two phases results in the formation of microvoids. The presence of such microvoids may be observed by microscopic inspection of the surface, and by the porosity which portions of the surface exhibit with respect to absorbance of liquids, which otherwise would be minimal. More than one low profile additive may be used.
It has been unexpectedly discovered that the low profile additives are more effective if the molding pressure is reduced by 10-50% after the resin has gelled. Benefits of the technique are either more low profile additive effect, use of lower amounts of low profile additive to achieve the same result, or both these benefits.
The sheet molding compositions also contain a microvoid-reducing thermoplastic polymer. By the term xe2x80x9cmicrovoid-reducingxe2x80x9d is meant the reduction of microvoids on at least one surface of the compression molded door skin. The reduction of microvoids may be assessed by comparing the mineral spirits uptake of a compression molded product with an otherwise similar product prepared from a composition which does not contain the microvoid-reducing thermoplastic polymer. A suitable microvoid-reducing thermoplastic polymer is one which causes a measurable reduction in the mineral spirits uptake under such circumstances. A variety of polymers are suitable for use as microvoid-reducing thermoplastic polymers, including polystyrene, polyethylene, copolymers of styrene and acrylonitrile, and aliphatic polyamides formed from longer carbon chain length monomers, and the like. In general, microvoid-reducing thermoplastic polymers tend to be non-polar polymers. Preferred microvoid-reducing thermoplastic polymers belong to the general class of sheet molding compound additives known as low shrinkage additives. More than one microvoid-reducing polymer may be used.
Low shrinkage additives are well known to those skilled in the art, and by contrast to low profile additives, have substantially less effect on microvoid formation. As with low profile additives, phase out during cure creates a multiphasic system. However, upon cooling, microvoid formation does not occur to a substantial extent. Rather the volume expansion which occurs during phase out contributes to maintenance of volume during the molding operation. Unlike low profile additives, low shrinkage additives are non-polar, or of relatively low polarity. Non-limiting examples include polyethylene, polystyrene, polyolefins in general, such as ethylene copolymers with other monomers such as hexene and octene, cyclohexene, and the like, polypropylene and polypropylene copolymers, and saturated polyesters having appreciable methylene chain lengths such as polycaprolactone. Polystyrene and polyethylene are preferred. Toughened polymers such as high impact polystyrene, and various modifications of the above polymers such as high density linear polyethylene, isotactic and atactic polypropylene and the like are suitable. More than one low shrinkage additive may be used.
In choosing a microvoid-reducing thermoplastic polymer in a formulation, the formulator must consider the compatibility of the skin pigments and stain pigments with the microvoid-reducing thermoplastic polymer. For example, when using iron oxide pigments, best performance in stain pigment adhesion occurs when the microvoid-reducing thermoplastic polymer has a relatively high surface energy. For example, with polyolefins in particular, low pigment/microvoid-reducing thermoplastic polymer compatibility occurs with polyolefins having a low surface energy, such as homopolymeric polyethylene. Thus, with polyolefins, a surface energy above 38 mJ/m3, preferably above 40 mJ/m3 is preferred. These surface energies are preferred for non-olefin polymers as well. Acceptable adhesion, 4 or 5B, measured in accordance with ASTM-3359 after allowing time for full cure (ca. 7 days), decreases rapidly as surface energy decreases. The quantity of microvoid-reducing thermoplastic polymer must be reduced accordingly. At a point, the uniformity of staining ceases to be acceptable to the consumer, despite acceptable adhesion. A surface energy below 36 mJ/m3 is generally unacceptable. Blends of polymers having high and low surface energies may be used in certain instances.
Suitable pigments are preferably those which result in a medium to dark pigmented skin, for example skins having an L* value between 66-75 units, preferably 66-71 units, measured in accordance with the 0-100 CIELAB Opponent Color Scale of test method SAE J1545 color analysis at a reflectance of 45xc2x0 and an observer angle of 2xc2x0 with D65 illumination. A variety of natural and synthetic pigments, both organic and inorganic are suitable, inorganic pigments generally being preferred from a light stability viewpoint. Suitable pigments are, for example, the various iron oxide pigments and carbon black. Iron oxide pigments are commercially available in colors ranging from black through brown and red to yellow. Mixtures of various pigments, including lighter pigments such as titanium dioxide, may be used to create a variety of light to dark brown and brown-red tones to simulate woods such as cherry, oak, walnut, and mahogany. The pigments are generally supplied to the molding formulation as a pigment grind in a suitable grind vehicle, for example a minor amount of liquid polyester. Pigments are generally employed in amounts of up to 20 weight percent, more preferably 1 weight percent to 15 weight percent, and more preferably about 2 weight percent to 10 weight percent, these weight percentages based on the total weight of all non-fiberglass and non-filler composition components.
The sheet molding composition generally contains a catalyst in an amount effective to cure the sheet molding compound in a reasonable time. Such catalysts are heat activatable, and are well known, including azo compounds such as azobis-(isobutyryronitrile) (AIBN), peroxides, hydroperoxides, peroxyesters, peroxyketones, and the like. Such catalysts generally cure the curable polyester by a free radical mechanism, and may be broadly termed free radical polymerization initiators. Catalysts which are effective in the typical compression molding temperature range of 100xc2x0 C. to 200xc2x0 C., preferably about 150xc2x0 C., are preferred.
Plasticizers may be used in the subject compositions where necessary. Preferably, plasticizers used will have a low vapor pressure and/or exhibit suitable solubility in system components such that the plasticizers will be substantially non-fugitive, i.e., will remain in the door skins even when subjected to relatively high temperatures as might be experienced by the exterior of a door exposed to sunlight through a glass storm door. Examples of suitable plasticizers include the various phosphate esters such as tricresylphosphate, low molecular weight polyester oligomers, and the like. Reactive plasticizers, for example, oligomeric saturated polyesters bearing a terminal or pendant site of unsaturation may be used as well.
Viscosity modifiers may also be used. Viscosity modifiers may include a number of ionic and non-ionic surfactants, associative thickeners, high molecular weight polyacrylic acid and polyacrylic acid copolymers, and the like. Such adjuvants are generally used in quantities of less than 5 weight percent, preferably less than 2 weight percent, and most preferably about 1 weight percent or less, these weight percents relative to the resin system component weight. Viscosity modifiers may increase or decrease viscosity as desired, or may introduce thixotropy into the composition.
Fillers are generally used in the subject invention. The amount of filler may range from 0 weight percent (no filler) to substantially in excess of 50% based on the non-fiberglass components. Amounts up to 75 weight percent have been found suitable, for example. Suitable fillers include various metallic oxides, hydroxides, carbonates, and the like. Suitable fillers also include various natural minerals including clays and finely ground limestone.
Fiberglass reinforcement or other fibrous reinforcement is necessary. While carbon fibers are currently too expensive to be commercially viable, such fibers are also well suited to the door skins of the present invention. By the term xe2x80x9cfibrous reinforcementxe2x80x9d is meant inorganic or organic reinforcing fibers which maintain their integrity at temperatures of at least 200xc2x0 C. and which are substantially non-soluble and non-swellable in the polyester sheet molding composition. Preferably, glass, carbon, or ceramic fibers or their mixtures are used. The fibers may be chopped (staple) fibers, continuous fibers, or mixtures of chopped and continuous fibers. Glass mat fibers such as are produced by needling or felting continuous fibers and/or staple fibers may be used as well.
A portion of the fiberglass may be substituted by mineral fillers without loss of significant physical properties. For example, it has been surprisingly discovered that up to about 25% or more of the fiberglass can be substituted by wollastonite, preferably up to 15%. When fillers such as wollastonite are used, they are added to the A-side curing resin system instead of separately and later as chopped fiberglass.
By the term xe2x80x9ccurable resin componentxe2x80x9d is meant the total of curable unsaturated polyester(s) and co-curable unsaturated monomer(s). By the term xe2x80x9cresin systemxe2x80x9d is meant the total of the curable resin component, low profile additive, and microvoid-reducing thermoplastic polymer. The term xe2x80x9cmajorxe2x80x9d as used herein means 50% or more on a weight basis. The term xe2x80x9cminorxe2x80x9d as used herein means less than 50% on a weight basis.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.